JPH0354550A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable uniform coating by incorporating a specified nonionic surfactant and a specified anionic surfactant into a silver halide emulsion layer or other hydrophilic colloidal layer. CONSTITUTION:A nonionic surfactant represented by formula I and/or a nonionic surfactant represented by formula II and an anionic surfactant represented by formula III are incorporated into a silver halide emulsion layer or other hydrophilic colloidal layer. In the formulae I, II, R<1> is 8-40C alkyl, alkenyl or aryl and each of R<2> and R<3> is H, 6-40C alkyl, cycloalkyl or aryl but R<2> and R<3> are not simultaneously H. In the formula III, R<4> is >= 6C alkyl or aryl. When a support is coated with a soln. contg. gelatin or other hydrophilic colloidal soln., uniform coating is enabled.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material containing a coating aid in a hydrophilic organic colloid coating layer. (Prior Art) As is well known, photographic materials consist of several layers of wood-philic colloid (usually gelatin) on a support such as plastic film or paper. These layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer, and a protective layer, and each layer contains various inorganic or organic additives in order to satisfy these functions. In this way, general photographic materials are made up of many hydrophilic organic colloid layers, and during their production, these coating solutions are coated with comet, repellent coating (comet and repellent will be described later), uneven coating, etc. It is required to apply a thin layer uniformly and at high speed without failure. In recent years, continuous and simultaneous multilayer coating has become popular as a coating method. The most difficult example of the coating process is the production of color photographic materials. In color photographic materials, many poorly water-soluble additives such as color couplers, ultraviolet absorbers, and optical brighteners are dissolved in high-boiling point solvents such as phthalate ester compounds and phosphate ester compounds to make them hydrophilic. It is used by dispersing (so-called emulsifying) a solution of an organic colloid, especially gelatin, in the presence of a surfactant and incorporating it into a hydrophilic organic colloid layer. If a large amount of surfactant is used as such an emulsifier, it becomes difficult to coat another hydrophilic organic colloid layer on top of the hydrophilic organic colloid layer. If the amount of emulsifier is reduced, the photographic properties of the photosensitive material after coating will become unstable. Various anionic surfactants have been used as coating aids for various coating solutions for photographic materials, and specific examples thereof include U.S. Pat. No. 2,240,476 and U.S. Pat.
No. 02, 3, 068. No. 10l, 3,22
No. 0,847, No. 3,415,649, West German patent 1,
No. 942,665, etc. On the other hand, although there are few specific examples of nonionic surfactants as coating aids, for example, Japanese Patent Publication No. 44-22659, No. 43
Examples include sig sugar derivatives disclosed in Japanese Patent No. 24722 and No. 41-13481, and the recently disclosed European Patent EP314425Ax. It is also widely practiced to coat a hydrophilic colloid aqueous solution containing a hydrophobic synthetic or polymeric substance (for example, acrylic acid ester) as a dispersion to form a layer constituting a photographic light-sensitive material. In such cases, it is also essential to use surfactants as emulsification and dispersion aids. (Problem to be Solved by the Invention) However, when coating a colloid liquid such as gelatin on a colloid layer such as gelatin using these anionic surfactants as a coating aid, it is difficult to remove the calcium contained in gelatin. Because the solubility of anionic surfactants is extremely reduced due to alkaline earth metal ions such as It had the drawback of significantly worsening the applicability. Also, US Patent No. 38506 used to prevent static electricity.
42, JP-A-57-146248, etc., cationic surfactants disclosed in JP-A-55-7763, JP-A-53
-92125, JP-A-5418728, etc., when a cationic antistatic agent such as a cationic polymer and an anionic surfactant as a coating agent for these are used together in the same photosensitive material, the same coating A major drawback is that when added to a liquid, the two form an insoluble complex, resulting in the formation of comets. On the other hand, regardless of the difference between coating aids and emulsification dispersion aids, even if they are added to a separate layer from the antistatic agent, both of them will dissolve into the processing solution when the photosensitive material is developed and will be insoluble in the processing solution. There was a problem that complexes were formed and uneven processing occurred. In recent years, it has been suggested that the amount of water used during treatment should be reduced from the standpoint of environmental conservation, water resources, cost, or simply making treatment equipment more compact. In addition, instead of a simple washing process with water, a method of reducing the amount of processing liquid by using a liquid containing various chemicals (for example, JP-A-57-8542, JP-A-57-8542;
B-14834, No. 57-132146, No. 58-
No. 1863l, No. 59-184345, No. 57-19
No. 7540 and No. 5B-134636). In this way, when reducing the amount of water used for washing or using chemicals, the surfactant that flows out from the photosensitive material may remain unevenly on the coating surface and discolor over time, or the high boiling point solvent dispersed in the coating may It is known that the so-called sweating phenomenon, which occurs when couplers etc. aggregate and coalesce, is promoted. In addition, in recent years, attempts have been made to reduce the amount of replenishment processing solution due to cost considerations, but in this case too, the proportion of surfactant accumulated in the processing solution increases, and the anionic surfactant that has been disclosed so far Continuing to process sensitive materials using these agents resulted in the formation of tar-like insoluble materials. Furthermore, in order to shorten the processing time, attempts were made to make the processing solution more concentrated, but this still had the same problems as above. As part of shortening and simplifying the processing time, bleach accelerators (JP-A-59-95630, JP-A-59-95630, JP-A-59-95630, JP-A-59-95630)
7-192953, Japanese Patent Publication No. 54-112056, and U.S. Pat. No. 4,552,834). However, it is known that an insoluble complex is formed between these bleaching accelerators and the aonic surfactant released from the sensitive material, causing contamination of the processing solution. In JP-A No. 54-98235, gelatin can be used even if alkaline earth metal ions such as calcium are contained therein by using an alkyl earth metal salt of a certain anionic surfactant into which ethylene oxide is introduced. It has been disclosed that a good coating property can be obtained. Although the use of alkylated earth metal salts of these anionic surfactants reduces coating failures such as repelling and provides somewhat better coating properties than conventional anionic surfactants, in recent years silver halide photosensitive materials have been However, it was not possible to satisfy the high-speed coating properties required for manufacturing. On the other hand, nonionic surfactants do not have the above-mentioned problem of ionic complex formation, but few of them show excellent effects in terms of -C suitability for high-speed coating, and polyester derivatives such as those mentioned above are It is only partially known. However, these methods were not sufficient for the high-speed simultaneous multilayer coating methods used in recent years. These problems may occur due to the properties of the surfactant itself used for each purpose, or due to interactions with other coexisting additives. Therefore, in order to solve these problems, it is considered most preferable to improve the individual surfactants used, but in practice this often results in a loss of the intended performance and poses significant difficulties. accompany. (Objective of the Invention) The first object of the present invention is to uniformly coat a gelatin-containing solution or other hydrophilic colloid solution onto a support such as film or paper or other photographic layers without comets or repelling. The objective is to provide a photographic material coated with In addition, comet is a book written by Deryagin et al., “Film Coating Theory J (B. M. Deryagin + S. M.
Levi, FilmCoating Theory
, The Focal Press, 196
4) P. As detailed in 183,
This refers to a phenomenon in which small amounts of oil particles, mineral oil particles, hydrophobic liquids, or solids contained in a coating solution form a core that is not coated locally, including the surrounding area. In addition, "hajii" refers to a phenomenon in which the coating solution does not spread sufficiently due mainly to surface tension, resulting in some areas not being coated. A second object of the present invention is to provide a photographic material that does not cause contamination of a developing solution or a roller. (Means for Solving the Problems) These objects of the present invention are to provide a nonionic surfactant [I] and/or [■] represented by the following general formula in a silver halide emulsion layer or other hydrophilic colloid layer. and the general formula (1113
The content of the anionic surfactant represented by (1) R'NI{Co(C
HOH). CHzO}1, where R1 has 8 to 8 carbon atoms
40 n represents an alkyl group, an alkenyl group, and an aryl group, and the alkyl group, alkenyl group, and aryl group may be further substituted with a substituent. Rz and Rs are each a hydrogen atom or an n-alkyl group having 6 to 40 carbon atoms:
It represents a cycloalkyl group or an aryl group, and the alkyl group, cycloalkyl group, or aryl group may be further substituted with a substituent. Furthermore, Rz and Bs cannot be hydrogen atoms at the same time, and n, m, and 1 are numbers from 3 to 6. (III) R' (B)p SOJ formula, R4
represents an alkyl group or an aryl group having at least 6 carbon atoms, and the alkyl group or aryl group may be substituted with W by a substituent. B represents a divalent linking group. P represents the number of O or l, respectively. M represents a cation. Preferred specific examples of Rl include (n)-
CslLt-Cllz (CI1!) scIIcIl
z n C+ zllxs (n}-
cl alls3CtHs R! , R' is preferably represented by n-CJ+x
- , (n}-C.Lt - , (n}-C+sll
z+ −(n←(:+zllts CHi(Cl
h) scIIcL-Cxls, etc. Preferred specific examples of R4 include (n}--C+ zllts (n'F-C+ alliz-?■11, C. II S, etc.). Preferred specific examples of B For example, 0 -O(CH.).- (a represents a number from 2 to 6) 0 - (CIICH.O(C112)T-1(R
, represents a hydrogen atom or one Rs C H 3 group, b represents a number from 1 to 30, and C represents a number from 0 to 6). Preferred specific examples of M include Na, K, Mg, NH4,
N (CxHs)4 etc. Next, specific examples of nonionic surfactants used in the present invention will be shown, but the present invention is not limited thereto. N-1 CI+3 (CIl1)! CIICIIZNHCO (C
HOH) 4 CH! O}l(n)-C+ tHtsNH
co(CHOH) aclIzoIIN-3 (n) C+J{+JHCO(CHOH)acHzOHN-4 CkIII *CHCHtNHCO(CHOH) 4C
IIEO}Il CJl? Next, specific examples of anionic surfactants that are preferably used together with the nonionic surfactants used in the present invention will be shown. C! HS i CH*COOCHzCI(CHx)icthA 3 CHxCOOCjl+ s (I1) CIICOOC6}1tko(n) SOsNa A-6 CbJ3CHCHxOSO3Na CIllll1? A-7 C+JssCONCHzCtlxSOsNaJ C11, A-8 0■ A-9 A ■ ■ C+ JtsOCH. CHCIltSO3Na011C. Ih. ．． As mentioned above, the nonionic surfactants represented by the general formulas [I] and [II] used in the present invention are not fully satisfactory as coating aids for coating solutions in high-speed simultaneous coating systems for photography. Ta. However, it has been found that a significantly superior coating effect can be obtained by using in combination with an anionic surfactant containing a sulfonic acid group or a sulfuric acid ester group represented by the general formula (III) used in the present invention.

In other words, it was found that uniform, high-speed simultaneous coating was possible without comets or bulges. Moreover, general formula [1] used in the present invention
], ([1) and ([[) The photographic film containing
It has also been found that this product has features such as being able to prevent the generation of contaminants in the processing solution. These reasons are because nonionic surfactants have many hydroxyl groups as hydrophilic groups in their molecules,
This is presumed to be due to complex surfactant behavior in combination with anionic surfactants that have sulfonic acid or sulfate groups in the molecule. The nonionic compounds represented by the general formulas [1) and [II] of the present invention can be easily synthesized by reacting an aliphatic amine with a lactone, such as gluconolactone. For example, US Patent No. 2,662,073, European Patent EP
In the present invention, compounds represented by general formulas [I], [II] and (Ill) can be used as coating aids in hydrophilic colloid coating liquids, which can be synthesized by the method described in No. 314425A2. It can be used by adding it inside.
The amount used is o. per kg of coating liquid. It can be added in an amount of oi to 50g, but preferably 0.05 to 5g. In addition, the ratio of the amount of nonionic surfactants represented by general formulas 2 [I] and [II] to the anionic surfactants represented by general formula (I[[) is nonion/'anion = 0.05.
~20, preferably 0,1. ~10. As for the method of addition, it is preferable to add the compound as a solution in water, methanol, or other water-miscible solvent. The surfactant may be added to the coating solution for any photographic layer covering the photographic light-sensitive material, regardless of whether the layer is a photosensitive layer or a non-photosensitive layer.

In the light-sensitive material of the present invention, by adding the compound of the above general formula, an extremely uniform coating film of hydrophilic colloid is formed not only at low speeds but also at high speeds.

In other words, uneven coating, comets, and repelling of the coating film do not occur. The present invention is particularly useful as a coating aid when a photosensitive material contains a lipophilic substance such as a coupler, alkylhydroquinone, an ultraviolet absorber, a sensitizing dye, or a hydrophobic vinyl polymer. That is, a solution obtained by dissolving these lipophilic substances in a high boiling point water-refractory solvent is mixed with hydrocolloid water in the presence of a surfactant of the general formula above. It can be finely and stably dispersed in a coating solution and used directly as a coating solution, or it can be further added to a coating solution such as a photographic emulsion.

On the other hand, it is also effective when preparing an aqueous dispersion of hydrophobic vinyl polymer. That is, when a hydrophobic vinyl monomer is emulsified in an aqueous solution containing a surfactant according to the present invention, and then a polymerization initiator M is added and polymerized, a stable aqueous dispersion with fine particle size can be obtained. As the hydrophilic organic colloid in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin,
Proteins such as casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, and derivatives such as sodium alginate and starch derivatives; A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of methacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull, Sac, Sci. Photo,
Japan. Enzyme-treated gelatin as described in Ko 16, p. 30 (1966) may be used, and gelatin hydrolysates and enzyme-containing M products may also be used. As gelatin derivatives, those obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, and maleimide compounds are used. ．． The hydrophilic organic colloid layer in the present invention is
A photographic coating layer containing the above-mentioned hydrophilic organic colloid, especially gelatin, as a binder, such as a silver halide emulsion layer, a surface protective layer, a filter layer, an intermediate layer, an antihalation layer, an antistatic layer, an undercoat layer, Examples include packing layers. The compound used in the present invention has high solubilizing power and high surface activity, so it is suitable for coating a hydrophilic organic colloid layer in which slightly water-soluble photographic additives are dissolved and dispersed using a high boiling point organic solvent. Preferably used.
Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.
Silver iodobromide containing 2 to 20 mol % of silver iodide and silver chlorobromide containing IO to 50 mol % of silver bromide are preferred. There are no limitations on the crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or tetradecahedral. They may be tabular grains having a thickness of 0.5 microns or less, a diameter of at least 0.6 microns, and an average aspect ratio of 5 or more, as described in Research Disclosure 22534. The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or different silver halides may be bonded by epitaxial bonding, You may be careful not to mix particles of various crystal forms. Furthermore, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle. The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good. These silver halide grains can be produced by known methods commonly used in the art. The silver halide emulsion is subjected to conventional chemical sensitization, that is,
Sensitization can be done by sulfur sensitization, noble metal sensitization, or a combination of these. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Pigments that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, hescyanine, logocyanine, merocyanine, oxonol, and hexioxonol, and one type or a combination of two or more types can be used. can. Examples of poorly water-soluble photographic additives used in the present invention include oil-soluble color couplers, antioxidants used to prevent color fogging or color mixing, and antifading agents (e.g., alkylhydroquinones, alkylphenols, chromans, etc.). , coumarons, etc.), hardeners, oil-soluble filter dyes, oil-soluble ultraviolet absorbers, DIR compounds (e.g., DI.R hydroquinones, colorless DIR compounds, etc.), developers, dye developers, DRR compounds, DDR couplers, etc. Among these, oil-soluble color couplers include naphthol or phenol compounds, virazolone or virazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Compounds that release a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image during development can be used. A typical example of such a compound is British Patent No. 2.09
No. 7,140 and No. 2,131,188, and is a coupler that releases a development accelerator through a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler. .

It is preferable that the development accelerator released from the DAR coupler has an adsorption group for silver halide.
No. 638 and No. 59-170840. Particularly preferred are DAR couplers that produce N-acyl-substituted hydrazines having a monocyclic or fused heterocycle as an adsorption group, which is detached from the coupling active site of a photographic coupler with a sulfur atom or a nitrogen atom. A specific example of such a coupler is described in Japanese Patent Application No. 58-237101.

Compounds described in JP-A-60-37556 which have a development accelerator moiety in the coupler residue, or JP-A-60-107029 which releases a development accelerator etc. through an oxidation-reduction reaction with a developing agent. The compounds described in can also be used in the photosensitive material of the present invention. The DAR coupler is preferably incorporated into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention.
No. 9-172640 or Japanese Unexamined Patent Publication No. 1-128429
It is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers as described in No. Even if it contains color-fogging preventive agents or color-mixing preventive agents such as hydroquinone derivatives, aminophenol derivatives, pulps, gallic acid derivatives, catechol derivatives, ascorbic #1 derivatives, colorless couplers, sulfonamide phenol derivatives, etc. good. Examples of high-boiling organic solvents used in the present invention include phthalic acid alkyl esters (dibutyl phthalate, dioctyl fucrate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl phosphate, etc.). butyl phosphate), citric acid esters (eg, acetyl tributyl citrate), benzoic acid esters (eg, octyl benzoate), and alkyl acids (eg, diethyl lauryl amide). In addition to the above, the hydrophilic colloid coating solution used in the present invention also contains stabilizers, hardeners, dyes, matting agents, photosensitive silver halide particles, other surfactants, polymer latex, optical brighteners, and others. It can contain various additives useful for photographic materials. Among these, nonionic surfactants are preferred as other surfactants to be used in combination with the surfactant used in the present invention. In the present invention, various known coating methods such as dip coating, roller coating, air knife coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers. can do. When applying multiple layers simultaneously, US Patent No. 2,681,294,
By the coating method described in the same No. 2761791, the same No. 3526528, the same No. 3508947, etc.
It can be applied. In particular, multi-slide coating methods such as U.S. Pat.
The present invention is effective for curtain coating methods such as those disclosed in No. 0 and No. 49-24133.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples. Example 1 Silver chlorobromide emulsion (containing 100 g of gelatin per 1 mole of halide) grain-formed and ripened in a conventional manner.
g was diluted 3 times with a 10% aqueous gelatin solution, and 2 g of sabonin was added per 1 kg of this emulsion solution. Separately from this emulsion solution, prepare a 5% aqueous gelatin solution and add
- An emulsion obtained by dispersing hexyroof phosphate in gelatin (average particle size: 0.9μ) was added as tri-n-hexyroophosphate to make 18cc/1kg of 5% aqueous gelatin solution. I made a liquid. l of this liquid
Divide into equal parts and add coating aid 2.0 to each as shown in Table 1. O
A 5% g/kg aqueous gelatin solution was added to prepare a coating solution for surface preservation. However, in the case of the present invention, the amount added was a nonion/anion ratio of 1/1, and a total of 12.0 g/kg of a 5% gelatin aqueous solution. The surface tension of this surface Wt layer coating solution was measured using the Wilhelmy hanging plate method (for example, E. Matijevich "Surfa").
ceand Call old Science''No.
Volume, pp. 124-128-i1ey-Tnrersc
(1969)). On the other hand, samples-[I] to (4) were prepared by simultaneously coating the emulsion solution and the coating solution for the surface protective layer on a cellulose triacetate support using a multi-slide method. I checked the number of comets. The results obtained are shown in Table 1. Measurement of degree of roller contamination Sample #1 coated with emulsion layer and surface retaining material was heated to 30.5C.
IIX17, IC1 cut into 1 corner. After uniform exposure so that the optical density after development becomes 1.0, automatic development processing (with silicone roller conveyor) (Developer: Fuji Photo Film RD-I 135°C, fixing bath: Fuji Photo Film) 50 sheets were continuously developed in a Fuji film (35° C., consisting of 3 baths including a water washing bath).

After thoroughly drying the water-washed squeeze roller, the occurrence of streak-like density unevenness occurring at the tip of the 51st sample was examined. The degree of roller contamination was evaluated according to the following four-level criteria. No unevenness in all degrees was observed. B: Slight density unevenness occurs. C: Considerable density unevenness occurs. D: Significant 4 degree unevenness occurs. Compound N 2 (n) C+zlhsN11CO(CIIOH)4c
H*otlN 5 A-1 A-2 SOJa As is clear from Table 1, the sample using the nonionic/anionic surfactant of the present invention has less comet generation and less roller contamination. (Example-2) On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer as shown below was prepared.

(Mi weight of photosensitive layer) The coating amount is determined by the amount expressed in g/rd of silver for silver halide and colloidal silver, and the amount expressed in g/rd for the coupler additive and gelatin. For dye-sensitive dyes, the molar loss is expressed per mole of silver halide in the same layer. No. IJi (antihalation layer) Black colloidal silver ...0.
5 Gelatin ・・・・・・1.3
Colored coupler C-1 ・・・・・・0.
06 Ultraviolet absorber UV-1 ・・・・・・0
．． 1 above UV-2...0.2 Dispersion oil Oi1-1...0.01 Same as above Oi1-1...0. Ol desilvering accelerator BA-1 ...0.03 Surfactant SA-2 ...0.01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ ) ...0.15 Gelatin colored coupler C Dispersion oil Oil-1 Surfactant SA-2 3rd layer (first red-sensitive emulsion layer) Silver iodide emulsion (silver iodide 2 mol%, average Particle size 0.3μ) Gelatin sensitizing dye I Sensitizing dye■ Sensitizing dye■ Coupler C-3 Coupler C-4 Coupler C-8 Coupler C-2 Dispersion oil Oil-1 Same as above Oil-3 Surfactant SA-1 41st! (Second red-sensitive emulsion N) Silver iodobromide emulsion (silver iodide 5 mol%, ... silver 0.4 ...0.6 ...1. OXIO- '...3.OX10-'...IXIO-'...0
．． 06...0. 06...0. 04...O, 03...0.03...0.012...0. 02 2...1. ...0. ...O. ...0. Average particle size 0. Gelatin sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Coupler C-3 Coupler C-4 Coupler C-8 Coupler C-2 Dispersion oil Oi I-1 Same as above Oi1-3 Surfactant SA-1 5th layer (5th layer 3 red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide lO mol %, average grain size 0.7μ) ・・・・・・Silver 1.0 Gelatin ・・・・・・1.0 Sensitizing dye■
...IXIO-'Sensitizing dye H ...3X10-'Sensitizing dye ■ ...IXIO-'Coupler C-6 ...0, O5.
...0. 7...2.5...IXIO-'...3XlO-'...IXIO-'...0. 24...0. 24...0. 04...0. 04...0. 1 5 ・・・・・・0.02 ・・・・・・0. 05 5μ) Coupler C-7 Dispersion oil Off-1 Same as above Oi1-2 Surfactant SA-1 6th layer (middle N) Gelatin compound Cpd-A Dispersion oil Oil-1 Surfactant SA-2 7th layer (Middle N) 1 green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 4 mol%, average grain size 0.3μ) ・・・・・・0. Sensitizing dye■
・・・・・・5×1 sensitizing dye■
...0.3X1 sensitizing dye V
...2Xl gelatin
・・・・・・l. Cabler C-9
...0. Coupler C-5
...0. Cabler C-1
・Dan・0. Dispersion oil Of f-1 ・
...0. ...0. ...0. ...0, ...0.・・・・・・l. ...0. ...0. ...0. 30 0-4 0-4 0-4 0 28 03 03 5 Surfactant SA-1 8th layer (second green-sensitive emulsion N) Silver iodobromide emulsion (iodide! I5 mol%, average grain size 0. 5μ) Gelatin sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Coupler C-9 Coupler C-1 Coupler C-10 Coupler C-5 Dispersion oil Oil-1 Surfactant SA-1 9th layer (3rd green sense Emulsion Ji) Silver iodobromide emulsion (silver iodide 6 mol %, average grain size 0.7μ) ・・・・・・Silver 0.85 Gelatin ・・・・・・1. 0 sensitizing dye■ ...3.5X10-' sensitizing dye■ ...1.4X10-'
...10.4 ...0.8 ...5X10-'...2X10-'...0.3X10-' ... 0, 25...0. 03 ・・・・・・0.015 ・・・・・・0. O l ...0.2 ...0. 0 l 04 ・・・・・・O. Cobbler C-ll...0. Coupler C-12...0. Coupler C-13...0. Cobbler C-1 ・・・・・・0. Cabler C
-15...O. Dispersion oil○
il-1...0. Same as above ○if-
2...0. Surfactant SA-1
...0. 10th layer (yellow filter layer) Gelatin yellow colloid compound Cpd-8 Dispersion oil Of1-1 Surfactant SA-2 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (im4 mol of iodide %, average diameter 0.
3μ) ...Silver O. gelatin
・・・・・・1. Sensitizing dye■
・・・・・・2×1 coupler C-14
...O.・・・・・・l. ...O. ...O. ...0. ...O. Cobbler C-5 Dispersion oil Qj I-1 Surfactant SA-1 12th layer (second blue-sensitive emulsion layer) Iodobromide m<silver iodide 10 mol%, average grain size l. 5μ) Gelatin sensitizing dye ■ Coupler C-14 Dispersion oil Oi +-1 Surfactant SA-1 13th layer (1st protective layer) Gelatin ultraviolet absorber UV-1 Same as above UV-2 Dispersion oil Oil-1 Dispersion oil Oil-2 Surfactant SA-3 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ) ...0.07 ...0.2 ... ...0.04 ...Silver 0.5 ...0.6 ...I X 1 0-' ...0.2.5 ・...0. 07...0. 03...O. ...0. ...O. ...O. ...0. ...O.・・・・・・i艮0、5 Gelatin ・・・0.45
Polymethyl methacrylate particles (diameter 1.5μ) ...0. 2 Hardener H-1...0.4 Formaldehyde scavenger S-1...0.5 Formaldehyde scavenger S-2...0
．． 5 Surfactant SA-4 ...0.0
1 Surfactant M SA-5 ・・・・・・0
．． The sample prepared in the manner described above was designated as sample 201. Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below: BA l UV-2 Oil ■ Tricresyl phosphate Oi1-2 Dibutyl phthalate Oi1-3 Bis(2-ethylhexyl) phthalate Yoi ■ 2 OH NaO, S 5υ3Na C 3 C-5 C 15 C-6 C11, 1{. C C Clls C11! C(Cllz)s C 7 C 8 C-9 011 mo+. wt, about 20 C 10 C-1 1 0 0 0 C-1 2 C-13 Cl C-14 cp dA CpdB Sensitizing dye 1 Sensitizing dye ■ Sum of sensitizing dyes (CIlz) zsOJ'N (Cdls) ff increase Sensitizing dye■ Sensitizing dye V (CIlt)gsOJ-N(Czlls)z(Clhas
sO. H-N (Calls) z Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ S-2 ]1 ]1 H ■ CHz =CII SOz CHz CO
NIICllt? Il■=CIl-So■ CL-CONI+ CH! S l {1 1I 1 Nobini L Mutual J Bini Dan 1 Biniyo Clh (CL) +oCll=CHCHzSOJaSA
-5 CZ++S CHsCH (CHz) 40cOcHg1 CH3(:II (Cll.) .OCOCll -
SOJaC t II s Dan” 22 History CIF? SO■N(CsHt)CHzCOOKSA-7 ■CsF + ys(hNllCHHzCHzCIIzOC
l{zclIJ (Clh). (n) C+ illg
sNHco (CHOH) 4CH1011 trial #l202
Preparation: Fluorine-based cationic surfactant SA was used instead of surfactant (antistatic agent) SA-6 in the 14th layer of sample 201.
The sample was prepared in the same manner as Sample Fl}201 except that -7 was substituted. Preparation of Sample 203: It was prepared in the same manner as Sample 201 except that Compound 1N-2 used in the present invention was substituted for the surfactant 7FISA-4 in the 14th layer of Sample 201. Preparation of sample 204: Produced in the same manner as sample 202 except that the surfactant SA-4 in the 14th layer of sample 202 was replaced with Compound 1-N-5 used in the present invention. The coating solution given above was applied simultaneously in multiple layers using the multi-slide method, and the number of comets generated per square meter of the sample coated was determined. This photographic element was then exposed to 25 CMS using a tungsten light source with the color temperature adjusted to 4800°K using a filter, and then subjected to the following processing using an automatic processor. Table 2 (Note) Per 1 m length of photosensitive material at 35 m/m In the above processing steps, water washing (■) and (2) were performed using a countercurrent water washing method from ■ to ■. Color developer> Mother solution Replenisher Diethylene triacetic acid 1.0g 1.0gl-Hydroxyethylidene-1. 1 Diphosphonic acid 2.0g 2.2g Sodium sulfite 4.0g 4.4g Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl N-β-hydrokine ethyl ajuno) 2-Methyl Add aniline sulfate solution to adjust pH Bleach solution> Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonia water Ammonium nitrate 30.0g 1. 4g 32. Og 0. 7g 1. 3■ 2, 4g 2. 6g 4. 5g 1N 10. 00 5. 0g 11 10.05 Mother liquor replenisher 100g 1 10g 10, Og 7 100g 11.0g 5li 12.0g Add ammonium bromide water to pH <Fixer> 150g 170g 1 i 1 2 6.0 5.8 Mother liquor ethylenediamine 4 Disodium acetate Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (70%) 175af Water was added to pH. <Water wash> Ordinary water was used. <Stabilizing liquid> ll 1.0g 1.2g 4.0g 5.0g 4.6g 5.8g 6. 6 Mother liquor formalin (37% 1/v) 2. 0H1 polyoxyethylene replenisher 200d l1 6.6 Replenisher 3. 0a! ! p-monononyl phenyl ether (average degree of polymerization 10) 0.3g Add 0.45g water 11 If first, Table 2
The exposed color photosensitive material (35 m/m width) was continuously processed for 20 days at a rate of 20 m per day using an automatic processor having the tank capacity described in . The processed samples r{ obtained in this way were designated as 201i to 205-1, respectively. Next, the following rinsing liquids were used for washing ■ and ■ in Table 2, and the treatment was continued for 20 days in the same manner as in Table 2, except that the replenishment amount was changed to 27 m. The treated samples obtained by this process were designated as 201-11 to 205-II. <Washing solution B> Mother solution Replenisher 2-methyl-isothiapurin-3one 5-chloro2-methylisothiazoline-3one 1 0■ 10Ilg lO■ 10■ Add water lj! 11 Sodium hydroxide pH 7.0 pH 7.0 For each sample treated in this way, the presence or absence of peeling static marks (fogging due to static electricity sparks) caused by the roller before treatment was examined to check for unevenness in treatment concentration. The occurrence was evaluated in 4 stages using the same criteria as in Example 1, and the stain on the surface of the treated sample was further evaluated in the following 3 stages. A: No dirt adhesion B: Some dirt adhesion C: Significant dirt adhesion These results are shown in Table 3. Procedural amendment 1.

Display of incidents 1999 Patent Application No. lyorrr 2. name of invention Silver halide photographic material 3. person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide emulsion layer or other hydrophilic colloid layer contains the following: Nonionic surfactant [I] and/or [
II] and an anionic surfactant represented by the general formula [III]. [I]R^1NHCO(CHOH)_nCH_2OH
], [II] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1 represents an alkyl group, alkenyl group, or aryl group having 8 to 40 carbon atoms. R^2 and R^3 each represent a hydrogen atom, or an alkyl group having 6 to 40 carbon atoms, a cycloalkyl group, or an aryl group, and R^2 and R^3 cannot be hydrogen atoms at the same time. n, m, l are numbers from 3 to 6. [III] R^4-(B)_p-SO_3M In the formula, R^4 represents an alkyl group and an aryl group having at least 6 carbon atoms, and B represents a divalent linking group. P represents the number 0 or 1, respectively. M represents a cation.